EP0843707A1 - Melanges de recouvrement, procede de production et utilisation a des fins de revetement - Google Patents

Melanges de recouvrement, procede de production et utilisation a des fins de revetement

Info

Publication number
EP0843707A1
EP0843707A1 EP96927626A EP96927626A EP0843707A1 EP 0843707 A1 EP0843707 A1 EP 0843707A1 EP 96927626 A EP96927626 A EP 96927626A EP 96927626 A EP96927626 A EP 96927626A EP 0843707 A1 EP0843707 A1 EP 0843707A1
Authority
EP
European Patent Office
Prior art keywords
weight
component
coating mixtures
mixtures according
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96927626A
Other languages
German (de)
English (en)
Other versions
EP0843707B1 (fr
Inventor
Jürgen HERBER
Jan Mazanek
Karl-Heinz Käsler
Gebhard Wagner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Weilburger Lackfabrik J Grebe GmbH
Momentive Performance Materials GmbH
Original Assignee
Bayer AG
Weilburger Lackfabrik J Grebe GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19539446A external-priority patent/DE19539446A1/de
Application filed by Bayer AG, Weilburger Lackfabrik J Grebe GmbH filed Critical Bayer AG
Publication of EP0843707A1 publication Critical patent/EP0843707A1/fr
Application granted granted Critical
Publication of EP0843707B1 publication Critical patent/EP0843707B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
    • C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"

Definitions

  • the present invention relates to coating mixtures comprising, in the water-free state, at least one polysiloxane, at least one reactive inorganic filler, at least one inorganic material which forms a film as a melt and at least one reactive (oligo) silane, a process for the preparation and the use thereof.
  • heat-resistant coatings for example, temperature resistance up to 600 ° C with continuous and alternating stress, high resistance to temperature differences ( ⁇ T resistance), high flexural strength, color stability, resistance to corrosive influences, good drying properties, good adhesion , simple manufacturing process (high storage stability) and good manageability and usability in the usual processes, such as spraying, rolling, dipping or brushing
  • the object of the present invention was therefore to provide stable, low-solvent, organic-solvent-free coating mixtures based on polysiloxane, which can be used in particular as heat-resistant coatings and which are distinguished by an improved property profile compared to the prior art
  • the present invention thus relates to coating mixtures containing in the anhydrous state
  • G 0 to 5% by weight, preferably 0.1 to 3% by weight of a further additive or a mixture of several additives,
  • the content of D) is preferably at least 1% by weight of F), preferably at least 0.05% by weight.
  • component A) is preferably at least one hydroxyl- and / or alkoxy-functional polysiloxane, which with water or other solvents in a mixture with water forms emulsions.
  • Polysiloxanes for the purposes of the invention are, for example, copolymers of polysiloxane and polyester, polyether and / or polyepoxide (or mixtures thereof), as well as linear or branched organopolysiloxanes.
  • a polysiloxane resin or a mixture of several polysiloxane resins, as described in EP-A 512 418, p. 3, lines 14-52, is preferably used as component A).
  • Polysiloxane resins are particularly preferred which have a proportion of 10-80, preferably 20-70, particularly preferably 35-60% by weight of difunctional building blocks of the general formula
  • R denotes any organic radical with Si-C linkage.
  • Combinations of branched and linear polysiloxanes are also particularly preferred.
  • Component A) is preferably used as an aqueous emulsion.
  • the use of A) in an organic solvent is also possible, it only has ecological disadvantages.
  • Component A) can, however, also be present as a mixture of several aqueous emulsions. If component A) is used in the form of an aqueous emulsion, the siloxane content is between 5 and 80% by weight, preferably between
  • Component A) may, however, optionally contain other solvents in addition to water.
  • at least one emulsifier and / or a theological additive, for example a thickener should preferably be added. Both cationic and anionic emulsifiers can be used as emulsifiers.
  • Component A), which is in the form of an emulsion can contain emulsifiers, thickeners and also other auxiliaries in amounts of 0.5-15% by weight, preferably 1-6% by weight, particularly preferably 1.5-5% by weight. , contain.
  • component A) can contain 0-5% by weight, preferably 0-2% by weight, particularly preferably 0-1% by weight, of a bactericide or fungicide.
  • Component A) can consist of pure polysiloxanes and / or oils or can be present in the form of corresponding emulsions in water and in a mixture with water and other solvents.
  • Component A) additionally contain catalysts.
  • the catalyst content can be up to 1% by weight, based on component A), it being possible to use conventional condensation catalysts, such as organotin compounds, organotitanium compounds and organoaluminum compounds.
  • component B) comprises all reactive inorganic compounds or inorganic compounds modified with organic radicals which contain reactive groups and which can react with themselves and / or other components of the mixtures according to the invention.
  • component B) are silica sols, alkali water glasses, silica esters, organosiliconates, such as e.g. Sodium methyl siliconate, titanic acid ester, aluminates, zirconium aluminates, aluminum hydroxide and organically modified fillers of all kinds, which contain reactive groups in the sense mentioned above, e.g. Fillers containing epoxy, amino or unsaturated groups, e.g. Quartz, glass, talc, chalk.
  • fillers also includes substances which, as the solid compounds or
  • Reaction products are available.
  • liquid titanium acid esters act that are built into the coatings.
  • the reactive inorganic filler B) is preferably colloidal silica in the form of a silica sol, alkali water glasses in aqueous solution or in solid form, alkyl siliconate,
  • the colloidal silica preferably has a content of 5-60% by weight of SiO 2 , preferably 10-40% by weight, SiO 2 , particularly preferably 15-35% by weight of SiO 2 .
  • a reactive inorganic filler in the sense of the invention is also pyrogenic silica in powder form and colloidal silica in the form of silica sols.
  • the silica sol particles can too be surface modified by the known methods.
  • Modified silica sol is also preferably used as component B), as described in DE-B 2 408 896, US-A 2 892 797, US-A 2 574 902, US-A 2 457 971, US-A 2 668 149 and US-A 2 650 200.
  • Silica sols with a particle size of 5-100 nanometers are particularly preferred, very particularly preferably 10-30 nanometers.
  • component C) can be any inorganic, film-forming material in the melt.
  • the film-forming material (C) as a melt is preferably an enamel and / or a low-melting glass.
  • the low-melting glass and / or enamel in the sense of the invention should have a softening point below 600 ° C, preferably ⁇ 550 ° C, particularly preferably ⁇ 440 ° C but not below 200 ° C, preferably not below 300 ° C and particularly preferred not below 350 ° C.
  • the coefficient of thermal expansion of the low-melting glass and / or enamel should accordingly be adapted to those of the metallic substrate so that the coatings do not flake off when heated.
  • the thermal expansion coefficient of the low-melting glass and / or enamel should be at least 380 x 10 "7 / K, preferably> 400 x 10 " 7 / K (measured cubically, between 20 ° C and 400 ° C), with an expansion coefficient greater than 550 x 10 "7 / K is less preferred.
  • the use of low-melting physiologically questionable or toxic elements, such as lead, cadmium is less preferred.
  • the enamels and / or glasses according to the invention are commercially available enamel raw materials, such as borax (Na 2 B 4 O 7 x 5H 2 O), quartz powder,
  • Component D) in the sense of the invention is preferably a pigment, iron oxide and / or a mica.
  • a particularly preferred component D) is a pigment or filler in the form of an inorganic, organic and / or metallic
  • Substance or mixtures thereof e.g. Aluminum oxide, magnesium and calcium phosphates and / or carbonates, carbides, nitrides, magnesium oxide, aluminum hydroxide, titanium dioxide, silicon carbide, zinc oxide, aluminum bronze, tin and zinc dust, zinc phosphate, phthalocyanine blue, various spinels, carbon black, graphite etc.
  • Very particularly D) inorganic thermostable are preferred
  • Pigments and / or at least one inorganic filler such as e.g. Iron oxide, mica and titanium dioxide.
  • Component E) in the sense of the invention preferably comprises (oligo) silanes and / or their (partial) hydrolysates or mixtures of different (oligo) silanes and / or their (partial) hydrolysates. They can be in the form of their aqueous solutions and / or emulsions or dispersions. Solutions of component E) in water are very particularly preferred.
  • Preferred component E) are water-soluble partial hydrolyzates of functional silanes, such as silanes containing amino groups, epoxy groups and / or hydroxyl groups, such as 3-aminopropyltris alkoxysilane, epoxypropyltrisalkoxysilane, 3-hydroxypropyltrisalkoxysilane and carboxyl-containing silanes.
  • functional silanes such as silanes containing amino groups, epoxy groups and / or hydroxyl groups, such as 3-aminopropyltris alkoxysilane, epoxypropyltrisalkoxysilane, 3-hydroxypropyltrisalkoxysilane and carboxyl-containing silanes.
  • the preferred components F) are the catalysts which accelerate condensation reactions. Catalysts for the reaction of hydroxyl groups in silanols or for the reaction of
  • Silanols with alkoxy silane groups e.g. organometallic compounds of tin.
  • component F are dibutyltin dilaurate or dibutyltin dioctoate.
  • Component G) can also be any additive known for the production of lacquers and paints, e.g. Fillers and pigments, mica,
  • Paint additives such as dispersing, leveling, thickening, defoaming and other auxiliaries, fungicides, bactericides, stabilizers, inhibitors and catalysts.
  • G) can also be a polymer or a mixture of several polymers, such as cellulose, polyether, polyacrylates, polyurethanes, plasticizers and various inorganic resins.
  • the coating mixtures of the invention may contain as component G) and organic, organometallic and / or inorganic corrosion inhibitors, such as phosphoric acid derivatives, various amines, azole substituted Benzoltri-, Nitrosophthal Acidsalze, Talmin, zinc salts of organic Stickstoffsäsuren such as Alcophor ® 827 from Henkel), substituted Phenols or similar or wetting agents.
  • organic, organometallic and / or inorganic corrosion inhibitors such as phosphoric acid derivatives, various amines, azole substituted Benzoltri-, Nitrosophthalklaresalze, Talmin, zinc salts of organic Stickstoffsäsuren such as Alcophor ® 827 from Henkel), substituted Phenols or similar or wetting agents.
  • the present invention also relates to coating mixtures obtainable from:
  • the present invention also relates to a process for the preparation of the coating mixtures according to the invention, according to which the amounts according to the invention
  • component B is presented as an aqueous dispersion
  • optionally wetting agents as component G), optionally non-reactive inorganic pigments, fillers and at least one component C) are stirred into the aqueous dispersion from component B) and then preferably stirred for 5 to 60 minutes,
  • Component E) and optionally further components G) are added with stirring and then at least one component A) and optionally component F) and optionally further components G), the sum of all components G) being 0 to 5% by weight, with stirring be added.
  • the coating mixtures are particularly preferably produced by the process according to the invention. This process improves both the properties of the coatings and the quality of the lacquers / paints from which the coatings according to the invention are produced. In a particularly preferred embodiment of the present invention, the amounts according to the invention
  • wetting agents component G
  • non-reactive inorganic pigments component D
  • component C component C
  • component A) and optionally catalyst (component F)) and optionally further components G) are finally component A) and optionally catalyst (component F)) and optionally further components G), the sum of all components G) being 0 to 5% by weight, added and stirred for 5 to 60 min, preferably 10 to 30 min
  • the methods used for the production of paints such as ball mills and other intensive mixing processes, are preferred.
  • various auxiliaries in particular dispersants, such as polyacrylic acid derivatives, polyphosphates, phosphonocarboxylic acid derivatives, is preferred in the production of these coating mixtures
  • Various organic and inorganic compounds such as, for example, bentonites, celluloses, polyacrylates or polyurethane thickeners, can be used to stabilize the coating systems according to the invention and their components and to protect them from sedimentation
  • the dispersions from the mixtures according to the invention contain 20-90
  • the aqueous phase can optionally contain organic solvents
  • the present invention also relates to a method for producing
  • Coatings from the coating mixtures according to the invention the coating mixtures being applied to the material to be coated, if necessary predried at room temperature and then exposed to temperatures of 150 to 750 ° C., preferably 150 to 700 ° C. for 1 to 120 minutes.
  • the coating mixtures are preferably used in the form of an aqueous dispersion
  • heat-resistant materials can be used as materials to be coated, such as steel, aluminum and also other metals and their alloys, enamelled materials and metal-coated steels. Depending on the type and intended use, these materials can be used pretreated or untreated. Any pretreatment can be carried out using all known methods, such as, for example, blasting treatment
  • the coating mixtures according to the invention are preferably applied to a solid base by spraying, dipping, rolling and coating techniques.
  • coatings with a layer thickness of 5-300 ⁇ m, preferably 10-150 ⁇ m, particularly preferably 15-75, can be made in this way ⁇ m
  • the applied coating mixtures can also be predried at a higher temperature.
  • the coating mixtures predried at room temperature already have sufficient mechanical strength as a coating on the solid base to be transported, deformed and / or handled differently.
  • the final application properties only become apparent after thermal treatment achieved
  • either a short-term treatment at a higher temperature or, analogously, a longer treatment at a low temperature can take place.
  • the preferred temperature range is between 150 and 700 ° C., preferably between 200 and 600 ° C.
  • Treatment can be between 1 - 120 min, preferably 5 - 60 min
  • the present invention also relates to the use of the coating mixtures according to the invention for the heat-resistant coating of furnaces, mufflers, industrial systems and heat-resistant objects of any kind.
  • These heat-resistant coatings represent soft to very hard layers depending on the previous thermal treatment and differ in their properties fundamentally different from those of the raw materials used, since these have been selected so that they vary in temperature range Dimensions can react with each other.
  • the property profile of the coatings produced is very strongly dependent on the temperature selected. It is therefore possible to produce tailor-made coatings for every area of application.
  • Bayferrox 303T ® black iron oxide from Bayer AG
  • Bayhibit S ® sodium salt of a trifunctional phosphonic carboxylic acid from Bayer AG
  • the mixture is then stirred at 1800 rpm for 10 minutes.
  • component VII, component IV and component III are added with stirring in the following sequence and then 20
  • component IIb is then added with stirring and dispersed for 20 minutes, 4) finally component I and component VI are added and the mixture is stirred for a further 20 minutes
  • the measured quantity is the chipped film part in% after thermal treatment at a fixed time and temperature Temperature shock test:
  • the coated and pre-dried plate is exposed to a temperature of 600 ° C for 1 hour and then quenched directly in 20 ° C cold water. Measured variable: chipped film part in%.
  • Measured variable rust value according to DIN 53 210, the comparative examples and other coatings that already showed places after thermal stress are not tested.
  • the measured values mean:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Structural Engineering (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP96927626A 1995-08-08 1996-07-29 Melanges de recouvrement, procede de production et utilisation a des fins de revetement Expired - Lifetime EP0843707B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19529093 1995-08-08
DE19529093 1995-08-08
DE19539446A DE19539446A1 (de) 1995-08-08 1995-10-24 Beschichtungsmischungen, ein Verfahren zu ihrer Herstellung und ihre Verwendung für Beschichtungen
DE19539446 1995-10-24
PCT/EP1996/003337 WO1997006220A1 (fr) 1995-08-08 1996-07-29 Melanges de recouvrement, procede de production et utilisation a des fins de revetement

Publications (2)

Publication Number Publication Date
EP0843707A1 true EP0843707A1 (fr) 1998-05-27
EP0843707B1 EP0843707B1 (fr) 2002-10-16

Family

ID=26017523

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96927626A Expired - Lifetime EP0843707B1 (fr) 1995-08-08 1996-07-29 Melanges de recouvrement, procede de production et utilisation a des fins de revetement

Country Status (7)

Country Link
US (1) US6087438A (fr)
EP (1) EP0843707B1 (fr)
JP (1) JPH11510536A (fr)
AT (1) ATE226235T1 (fr)
ES (1) ES2185793T3 (fr)
TW (1) TW397856B (fr)
WO (1) WO1997006220A1 (fr)

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DE19814060A1 (de) * 1998-03-30 1999-10-07 Bayer Ag Borhaltige Mischungen, Hybridmaterialien und Beschichtungen
US6610777B1 (en) * 1999-07-30 2003-08-26 Ppg Industries Ohio, Inc. Flexible coating compositions having improved scratch resistance, coated substrates and methods related thereto
JP2003506518A (ja) * 1999-07-30 2003-02-18 ピーピージー インダストリーズ オハイオ， インコーポレイテッド 改良ひっかき抵抗性を有するコーティング組成物、コート基材及びそれに関連する方法
CA2380412A1 (fr) 1999-07-30 2001-02-08 Lawrence G. Anderson Compositions de revetement presentant une resistance amelioree au egratignures, substrats revetus et procedes correspondant
GB9929085D0 (en) * 1999-12-09 2000-02-02 Safeguard Chemicals Limited Composition and method for the treatment of concrete and masonry
ATE382589T2 (de) † 1999-12-09 2008-01-15 Safeguard Chemicals Ltd Zusammensetzung und verfahren zur behandlung von beton und mauerwerk
US6932862B2 (en) * 2001-11-29 2005-08-23 Maytag Corporation High temperature coating composition and method of applying
FR2862122B1 (fr) * 2003-11-10 2010-12-17 Pcx Materiau isolant thermique
MXPA06010676A (es) 2004-03-19 2007-02-21 Doerken Ewald Ag Microrevestimiento comprendiendo siloxanos.
WO2006016509A1 (fr) * 2004-08-09 2006-02-16 Nippon Steel Chemical Co., Ltd. Composition de résine époxyde et composition de revêtement d’époxy-polysiloxane
KR100562748B1 (ko) * 2004-11-06 2006-03-20 티오켐 주식회사 표면처리제 조성물
EP2008329B1 (fr) * 2006-04-12 2017-09-06 Sampath Kumar Thothathri Dispersion électrochimique nanoscopique pour batteries rechargeables alcalines au zinc
US20080090948A1 (en) * 2006-10-12 2008-04-17 Dewitt Julie Waterbased low noise generating coating
US8563648B2 (en) 2009-10-28 2013-10-22 Ppg Industries Ohio, Inc. Coating composition comprising an alkoxysilane, a polysiloxane, and a plurality of particles
KR20130060191A (ko) * 2010-04-30 2013-06-07 바텔리 메모리얼 인스티튜트 표면 세정이 용이한 조성물
EP2700682A1 (fr) 2012-08-21 2014-02-26 Uwe Lungmuß Revêtement dissipant la chaleur, notamment pour des creusets de fonderie ou des échangeurs de chaleur
DE102012107686B4 (de) * 2012-08-21 2016-06-16 Uwe Lungmuß Wärmeableitende Beschichtung, insbesondere für Gießereipfannen

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Also Published As

Publication number Publication date
JPH11510536A (ja) 1999-09-14
ATE226235T1 (de) 2002-11-15
WO1997006220A1 (fr) 1997-02-20
EP0843707B1 (fr) 2002-10-16
US6087438A (en) 2000-07-11
TW397856B (en) 2000-07-11
ES2185793T3 (es) 2003-05-01

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